Insecticidal composition comprising a synergistic mixture of 5 - benzyl - 3-furylmethyl d - trans-chrysanthemate and n-(3,4,5,6 - tetrahydrophthalimido)-methyl d-trans-chrysanthemate

ABSTRACT

AN INSECTICIDAL COMPOSITION HAVING LOW TOXICITY AND RAPID EFFECT WHICH COMPRISES, AS AN ACTIVE INGREDIENT, A MIXTURE OF 5-BENZYL-3-FURYLMETHYL D-TRANS-CHRYSANTHEMATE AND N-(3,4,5,6-TETRAHYDROPHTHALIMIDE)-METHYL D-TRANSCHRYSANTHEMATE.

Nov. 14, 1972 KEIZO HAMURO 3,702,891

INSIJC'I'ICIDAL COMBOSITION COMPRISING A SYNERGISTIC MIXTURE OF5-I3ENZYL5-FURYLMETHYL D-TRANS-CHRYSANTHEMATE AND (5,4,5,

THETRAHYDROPHTHALIMIDO -METHYL D-TRANS -CHRYSANTHEMATE Filed Nov. 17,1970 5 Sheets-Sheet 1 THEU/PEf/CAL 50 Faun/0 :0 I l l l I COMPOU/VDU Q Q5 Z 9 95/0 COMOOIJ'VDWJ b 525 9 7 5 3 0 5 0 INVENTOR K E l 20 HAM U R0BY 1 M gm TTORNEYS Nov. 14, 1972 KEIZO HAMURO 3,702,891

INSECTICIDAL COMPOSITION COMPRISING A SYNERGISTIC MIXTURE OF5-BENZYL-5-FURYLMETHYb D-TRANS-CHRYSANTHEMATE AND (3,4,5,

TRETRAHYDROPHTHALIMIDO -METHYL D-TRANS -CHRYSANTHEMATE Filed Nov. 17,1970 3 Sheets-Sheet 2 L650 mg //00ml THEOREUCAL FOUND COMFUU/VOUPQ @5/ a5 7 9 95/0 MH) /0 95 9 7 5 3 i 05 b MIX/N6 RAT/0 INVENTOR KEIZO HAMUROORNEYS Nov. 14, 1972 KEIZO HAMURO 3,702,891

INSECTICIDAL COMPOSITION COMPRISING A SYNERGISTIC MIXTURE OF5-BENZYL-f5-FURYLMETHYL D-TRANS-CHRYSANTHEMATE AND (s,4,s,e-

TRETRAHYDROPHTHALIMIDO)-METHYL D-TRANS-CHRYSANTHEMATE Filed Nov. 17,1970 r 5 Sheets-Sheet 5 FIG 3 INVENTOR KEIZO HAMURO United States PatentOflice 3,702,891 Patented Nov. 14, 1972 3 702 891 INSECTICIDALCOMPSI'fION COMPRISING A SYNERGISTIC MIXTURE OF BENZYL 3- FURYLMETHY L dTRANS-CHRYSANTHEMATE mixtureof said two compounds can display markedsynergistic actions not only in K.D. effect but also in killing effectwhich cannot be easily inferred from other mixtures and which cannot beeasily elucidated theoreti- 5 cally. AND N- 3 4 5 6TETRAHYDROPHTHALIMIDO} wmmihfrkANs-cfiRYsANTtmMATE k 1.3" i i??? r fiiam iifiin5 3302.55? Keizo Hamuro, Nishinomiya, Japan, assignor to 7 own6 ecs o e e c p sumitom Che i l Company, L Osaka, Japan tiles, FIG. 2shows the killing efiects thereof on housefhes, Filed Nov. 17, 1970,Ser. No. 90,412 and FIG. 3 shows the killing effects thereof on northernClaims priority, application Japan, Nov. 19, 1969, 10 house mosquitolarvae, all of which effects are repre- 44/93,287 sented by measuredvalues and by theoretical values cal- Illt- A0111 9/ 9/ 28 culatedaccording to the Yun-Pei Sun method. CL 424-274 1 Clan The synergisticactions attained by mixing the compound (I) with the compound (II) areexplained below ABSTRACT OF THE DISCLOSURE 5 with reference toexperimental examples. A ticidal composition having low toxicity andEXPERIMENTAL {EXAMPLE 1 11 msec rapid effect which comprises, as anactive ingredient, a The compounds (I).and (H) mdlvldually forum mixtureof s benzyl 3 furyhnethyl d trans chrysanthfimate lated by use ofdeodorrzed kerosene into 0.005%, 0.01%, and N-(3,4,5,6-tetrahydrophthalimide)-methyl d-trans 095% 097% (109%, andChrysanthemum solutions. In the same manner as above, there wereformulated 0.1% 011 solutions of individual mlxtures comprising thecompound (I) and the compound (II) in This invention relates to aninsecticidal composition such ratios as 0.5 :9.5, 1:9, 3:7, 5:15, 7:3,9:1 and 9.5 :0.5. prepared by mixing two kinds of known chrysanthemateOn the other hand, housefly adults, which had elapsed type insecticides,thereby overcoming the drawbacks of 3-5 days after emergence, wereliberated in a (70 cm?) the individual insecticides and making itpossible to synerglass chamber. Into this glass chamber, 0.7 ml. of eachgistically increase the insecticidal effects thereof. of the samplesprepared in the above was sprayed under More particularly, the presentinvention pertains to a pressure of 100 pounds p.s.i. by use of anatomizer. an insecticidal composition having rapid knockdown effectSubsequently, the K.D. of the housefly adults was ob- (hereinafterabbreviated to K.Df) and prominent killing served with lapse of time tomeasure the time required effect, the said composition being prepared bymixing for K.D. (hereinafter represented by KT TheS-benzyl-3-f'urylmethyl d-trans-chrysanthemate [hereinresults were asset forth in Table l, and thus the two after referred to as the compound(I)] and N-(3,4,5,6- compounds obviously showed synergistic effects inK.D. tetrahydrophthalimide)-methyl d-transchrysanthemate 35 Each of thevalues in the table is an average of runs [hereinafter referred to asthe compound (II)], and the repeated 5 times.

TABLE 1 Oil solution of compound (II) Oil solution of compound (I) andcompound (II) K.D. efiect on housefiies Oil solution of compound (I)Mixing proportion KTsn Concen- Mixing ratio of Concen- Concentra- KT(sec.)

Concentration KT tration KT compound (I): tration KTEU Compound Compoundtion of oil (see) theorct- (percent) (sec) (percent) (see) compound (11)(percent) (see) (I) (11) (percent) found feel I 0. 0. 095 57 0. 5:9. 50. 1 52 0. 5 9. 5 0. 1 52 57 0. 0. 09 66 1:9 0. 1 53 1 9 0. 1 53 59 0.0. 07 92 3:7 0. 1 58 3 7 0. 1 I 58 70 0. 0.05 5:5 0. 1 70 5 5 O. 1 70 870. 0. 03 219 7 :2 0.1 95 7 3 0. 1 95 113 0. 0. 01 440 9:1 0. 1 142 e 10. 1 142 161 0. 0. 005 600 9. 5:0. 5 0. 1 164 9. 5 0. 5 0. 1 164 0. 10 00.1 204 204 1 The theoretical values were calculated according to theYun-Pei Sun method.

mixing ratio of the compound (I) to the compound (II) being within arange between 9.5 :05 and 0.5 :9.5.

The compound ('II) is a low toxic insecticide having an extremely rapidK.D. efiect on so-called sanitary injurious insects such as housefiies,mosquitoes, cockroaches, etc. and on agricultural injurious insects, andthe K.D. effect thereof is the most excellent among the chrysanthematetype compounds. However, the compound (II) has such drawback that whenused singly, it is not always prominent in killing effect.

On the other hand, the compound (I) has an extremely strong insecticidalactivity, i.e. killing effect, on sanitary and agricultural injuriousinsects, and is markedly low in toxicity to mammals. However, thecompound (-I) is very low in K.D. effect, and hence is not usable as adomestic insecticide which is required to be rapid in K.D. effect, inpractice.

As the result of extensive studies made for years on strong insecticideswhich are low toxic and quick-acting, the present inventor has foundthat when the compound (I) is mixed with the compound (II), thedrawbacks of the two compounds are overcome and, surprisingly, the

From the above table, it is evident that when the compound (I) and thecompound (II) are mixed-each other in various proportions, the resultinginsecticides are synergistically increased in K.D. effect. In order tofurther clarify the above-mentioned fact, the measured values set forthin Table 1 (No. l) are shown in Table 1 (No. 2) together withtheoretical values calculated according to the Yun-Pei Sun et al. method[J. Econ. Entomol. 53, pp. 887-89l (1960)] which is ordinarily employedin examining whether or not two chemicals used in admixture come to showa synergistic effect. Further, the said values may be represented by thecurves shown in FIG. 1. Since the curve representing the measured valuesis below the curve representing the theoretical values calculatedaccording to the Yuri-Pei Sun method, it is substantiated that theinsecticides comprising the compounds (I) and (II) have excellentsynergistic effects.

EXPERIMENTAL EXAMPLE 2 The compound (-I), the compound (II) and mixturescomprising the compounds (I) and (II) in such ratios 3 as 0.5:9.5, 1:9,3:7, 5:5, 7:3, 9:1 and 9.5:0.5 were individually formulated into oilsolutions at various test concentrations. These oil solutions wereindividually measured in L value (50% lethal concentration) according tothe Campbells turn table method [Soap 3 and FIG. 3, and it is evidentfor the reason mentioned previously that the mixed insecticidescomprising the compounds (I) and (II) in various mixing proportions haveexcellent synergistic effects.

TABLE 3 and Samtary Chemlcals, vol. 14, No. 6, 119 (1938)]. Lethalefiect on northern Subsequently, from the LC values of the compound (I)Mixing proportion house mosquitoes and the compound (II), theoretical LCvalues of the Measured Theoretical mixtures comprising the two compoundsin various mix- Compound Compound Lo l lvalue lng proportions werecalculated according to the aforesaid 10 (up- (p-n- Yun-Pei Sun method.0 10 0.0356 0. 0355 The theoretical values and the measured values are-3 8852 8-8??? shown in Table 2. As is clear from the table, themeasured 3 7 010186 010245 values are more excellent than thetheoretical values g 8-8122 g-gfgg no matter what mixing proportions areadopted, and 15 9 1 010140 0101 therefore it 1s understood that themixtures have been 13-0137 @0149 10 0 0. 0145 0. 0145 synergisticallyincreased also in lethal effect.

1 The theoretical values were calculated according to the Yun-Pei SunTABLE 2 method.

M v Lethal efiect on houseflies EXPERIMENTAL EXAMPLE 4 ixing propor ionM} LC JM The compound (I), the compound (II) and mixtures 3 (mg'l f figfigyl comprising the compounds (I) and (II) in a ratio of 1:1 0 1O 43 43were individually formulated 1nto 0.4% 'oll-based and O. 5 9. 5 2L7 3water-based aerosols, Each of the thus formulated aerosols g g 9-? 25was sprayed in an amount of 650:50 mg. into a (6 ft.)3 5 5 317 1 PeetGradys chamber. To the mist were exposed housefly g g adults, and theK.D. and insecticidal effects of the indi- 9.5 0.5 2: 3 215 vidualaerosols on the houseflies were observed.

10 0 The results were as shown in Table 4, and thus the The theoreticalvalues were calculated according to the aerosols containing the mixtureof the compounds Sun meflwdand (II) obviously displayed synergisticeffects.

TABLE 4 Sprayed K.D. (percent) amount Mortality Aerosol (mg/(6 ft.)5min. 10 min. 15 min. (percent) Oil-based aerosol of compound (I) 690 8.0 35. 8 83. 5 83. 5 Oil-based aerosol of compound (II) 690 34.1 69. 395. 4 40. 2 Oil-based aerosol of compound (1) plus compound (II) 655 26.7 61. 4 96.0 96.0 Water-based aerosol of compound (I) 670 6. 0 40. 9 86.8 86. 8 Water-based aerosol of compound (II) 635 36. 2 75. 5 97. 6 49. 3Water-based aerosol of compound (1) plus compound (II) 650 26.0 66. 098.0 98.0

From the above table, it is evident that the mixed insecticidescomprising the compounds (I) and (II) in various proportions had beensynergistically increased in lethal effect. In order to further clarifythe abovementioned fact, the measured and theoretical L0 values of themixed insecticides were represented by the curves as shown in FIG. 2,like in the case where the synergistic effects on K.D. effects weresubstantiated. As seen in FIG. 2, it is clear that the mixedinsecticides comprising the compounds (I) and (II) in variousproportions have been synergistically increased also in lethal eifect.

EXPERIMENTAL EXAMPLE 3 The compound (I), the compound (II) and mixturescomprising the compounds (I) and (II) in such ratios as 0.5:9.5, 1:9,3:7, 5:5, 7:3, 9:1 and 95:05 were individually formulated into 10%emulsifiable concentrates, which were then diluted with distilled waterto prepare test liquids at various test concentrations. Each 200 ml. ofthe test liquids was charged in a 300 ml. beaker, and last instar larvaeof northern house mosquitoes were liberated in the liquid. After 24hours, the alive and dead of the larvae were observed to measure the LCvalues (50% lethal concentrations) of the individual test liquids.

The measured LC values of the mixed test liquids were compared with thetheoretical values thereof calculated according to the aforesaid Yun-PeiSun method to examine whether or not the mixed test liquids hadsynergistic elfects. The results were as shown in Table The insecticidalcompositions of the present invention can be formulated into oilsolutions, dusts, emulsifiable concentrates, aerosols, granules,wettable powders and death-inducing powdery or solid preparationsincorporated with baits or materials attractive for injurious insects,and can be shaped into forms ordinarily applied to chrysanthemate typeinsecticides, such as mosquito coils, fumigants, etc. Further, they canbe easily prepared according to the ordinary procedures.

No matter what proportions are employed within a range of between 0519.5and 9.5 :0.5, the present compositions display strong synergisticeifects, but what proportion is to be adopted is dependent upon thepurpose of application of the resulting composition.

The present invention is illustrated in further detail below withreference to examples, but it is needless to say that the scope of theinvention is not limited by these examples.

EXAMPLE 1 0.2 g. of a homogeneous mixture comprising 1 part of thecompound (I) and 9 parts of the compound (II) was dissolved in 99.8 g.of deodorized kerosene to obtain an oil solution.

EXAMPLE 2 0.4 g. of a homogeneous mixture comprising 5 parts of thecompound (I) and 5 parts of the compound (II) was mixed with 7.1 g. ofxylene and 7.5 g. of deodorized kerosene, and the resulting mixture wascharged into an aerosol container. After attaching a valve portion tothe container, 85 g. of a propellant (e.g. Freon, vinyl chloride monomeror liquefied petroleum gas) was filled under pressure through said valveportion into the container to obtain an aerosol.

EXAMPLE 3 (e.g. felt), and then the methanol was removed by vaporizationto obtain an insecticidal sheet for electric heating. The thus obtainedsheet was placed on an electrically heated plate, whereby the samepurpose as that of a mosquito coil could be accomplished.

Insecticidal eifects of several of the present composith: 30: 2:11:d zii ggafi i ih22 2512335 32,: 8 Obtained in the above manner are shownbelow mixed with 13.6 g. of deodorized kerosene and 1.0 g. of Wlthreference to test examples Atmos 300 (registered trade name for anemulsifier pro- TEST EXAMPLE 1 duced by Atlas Chemical Industries,Inc.). The resulting Into a (78 cmfi) glass chamber were liberated aboutmlxture was emulslfiefl wlth addltlon of 9 of Pure 50 housefly adults,and 0.7 ml. of the oil solution obwater and then filled into an aerosolcontainer together tained in Example 1 was uniformly sprayed into thewith a 3:1 mixture of deodorized butane and deodorized chamber under aPressure of 10 pounds by use of a glass ProPane obtam a water'basedaerosolatomizer, whereby more than 90% of the housefiies could EXAMPLE 4be knocked-down within 5 minutes and more than 90% g. of a homogeneousmixture comprising 7 parts thereof could be klued on the next of thecompound (I) and 3 parts of the compound (II) TEST EXAMPLE 2 was mixedwith g. of Sorpol 2020 (registered trade name for an emulsifier producedby Toho Chemical Co.) 20 A P la5t1c s cylmder of 14 Inner dlalhetel' andand with 55 g. of xylene in this order to obtain a homo- 7 helghtcovered at h lower P Wlth a Wire geneous emulsifiable concentrate. net.Into the cylinder were liberated 10 cockroaches (Periplanetafuliginosa), and then the cylinder was cov- EXAMPLE 5 ered also at theupper part with a wire net. Subsequently, 50 g. of a homogeneous mixturecomprising 5 parts of 25 the Cylinder e Placed at the lower P Of aNagasthe compound (I) and 5 parts of the compound (II) was awas mistshtthhg apparatus (Sumio Nagasawai 3001111 thoroughly mixed with 1.5 g.of Sorpol 5029 (registered Kagakll (501611Ce of Insect Control)? PP-trade name for an emulsifier produced by Toho Chemical 192, and each ofthe aerosols Obtalhed ih Exam Co.) and with 3.5 g. of lignin. Theresulting mixture was P 2 and 3 was Sprayed dlrectly to the cockroachesthoroughly stirred together with 45 g. of diatomaceous through the upperof the apparatus- After Spraylhg earth in a mortar to obtain a wettablepowder. the aerosol, K.D. ratio of the insects was observed with lapseof time. 20 minutes thereafter, the cockroaches EXAMPLE 6 weretransferred to and fed in another rearing cage, and 1 g. of ahomogeneous mixture comprising 2 parts the alive and dead thereof wereobserved after 3 days. of the compound (I) and 8 parts of the compound(II) Th6 results as shown In Table TABLE 5 K.D. ratio with lapse of time(percent) iifiifiisitlfii da'ittii 5min. 7min. 10 1.11... 15mm. 20min.iiiititi 5 e0 100 100 100 tiiiiiiiiiiiiiiii :31? a 52 :2

1 OT Ofli 1 1T t Aer sol Oificial Test Aerosol oi the ChemicalSpecialties Manufacturers, U.S.A. That is, OTA ii a sta nharg aeros l ued throughout the world (or insecticidal effect test which has beenprepared by the Chemical Specialties Manufacturers Association of theU.S., and contains 0.4% of natural pyrethrln and 2% or DDT. wasdissolved in 30 ml. of acetone. The resulting solution was thoroughlykneaded in a mortar with 99 g. of 300 mesh diatomaceous earth, and thenthe acetone was removed by vaporization to obtain a dust.

EXAMPLE 7 TEST EXAMPLE 3 Each of an aqueous 200 times-diluted liquid ofthe emulsifiable concentrate obtained in Example 4 and an aqueous 500times-diluted liquid of the wettable powder obtained in Example 5 wasuniformly dropped by use of a pipet onto the surface of a (15 cm?)plywood so that the proportion of the liquid became 50 ml./m. and thendried in air. About 20 housefly adults were liberated in a cylindricalwire net of 9 cm. in diameter and 1 cm. in height, and were contactedwith the surface of the plywood treated in the above manner, and thenumber of knocked-down insects was counted with lapse of time. After 30minutes contact, the houseflies were transferred to and fed in a rearingcage, and the alive and dead thereof were observed after one day. Theresults were as shown in Table 6.

TABLE 6 K.D. ratio with lapse of time (percent) 2 min. MortalityInsecticidal composition 30 s c 5 min. 7 min. 10 min. 15 min. 20 min. 30min. (percent) 200 times-diluted liquid of the emulsifiablo concentrateof Example 4-- 59.0 76. 0 98. 0 100 100 100 100 100 500 times-dilutedliquid of the wettable powder of Example 5 72. 4 94. 0 97. 0 100 100 100100 solu i of Pyrethrin 0 2 36. a 75.8 as. 4 94. 7 98.9 30. 5

EXAMPLE 8 1 g. of a homogeneous mixture comprising 2 parts of thecompound (I) and 8 parts of the compound (II) was dissolved in 20 ml. ofmethanol. A given amount of TEST EXAMPLE 4 A glass Petri dish of 14 cm.in inner diameter and 7 cm. in height was coated on the inner wall withbutter, leaving at the lower part an uncoated area of about 1 cm. inwidth.

the resulting solution was dropped onto a fibrous material 75 Onto thebottom of the dish, the dust obtained in Example 6 was uniformly dustedin a proportion of 2 g./m. TABLE 9 Subsequently, 10 German cockroachadults were liberated if in the dish and contacted with the dust, andthe number of g t fi ggfi knocked down insects was counted with lapse oftime. Insecticidal composition -s p After 10 minutes, the cockroacheswere transferred to an- 5 Mosquito coil of Exqmple 7 100 other vessel,and the alive and dead thereof were observed Mosq 0011 aining 0.5%orallethrm-- 8'36" 29.8 after 3 days. The results were as shown in Table7.

TABLE 7 ED. ratio with lapse of time (percent) Insecticidal 1 min., 2min., Mortality composition 38 sec. 15 sec. 30 sec. 5 min. 10 min.(percent) Dust of Example 6 60. 0 100 100 100 100 100 TEST EXAMPLE 5TABLE 8 K.D. efiect Mortality sO) (kill Insecticidal eomposltion(min.-sec.) percent) Mosquito coil of Example 7 6'06 100 Mosquito coilcontaining 0.5% of allethrin. 6'24 56. 5 30 Further, housefly adultsweretreated in the same manner as above to obtain the KT values andmortality as shown in Table 9.

What is claimed is:

1. An insecticidal composition comprising an insecticidally effectiveamount of a mixture of 5-benzyl-3-furylmethyl d-trans-chrysanthemate andN-(3,4,5,6-tetrahydrophthalimido)-methyl d-trans-chrysanthemate, in aratio of between 0 .5:9.5 and 9.5 :0.5.

References Cited UNITED STATES PATENTS 3,268,551 8/1966 Koramoto et al.424-306 X 3,542,928 11/1970 Elliott 424-306 X OTHER REFERENCES J. Econ.Entomology 53, 887-91 (1960).

ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner US.Cl. X.R.

